US4546124A - Polyurethane binder compositions - Google Patents
Polyurethane binder compositions Download PDFInfo
- Publication number
- US4546124A US4546124A US06/660,170 US66017084A US4546124A US 4546124 A US4546124 A US 4546124A US 66017084 A US66017084 A US 66017084A US 4546124 A US4546124 A US 4546124A
- Authority
- US
- United States
- Prior art keywords
- phenol
- resin
- prepared
- resole resin
- modified phenolic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2273—Polyurethanes; Polyisocyanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/542—Polycondensates of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
Definitions
- This invention relates to binder compositions, moldable compositions which include the binders and aggregate material, cores or molds made from the moldable compositions, and a process for making them. More particularly, the invention relates to foundry binder compositions, moldable compositions including the same, and aggregate material in foundry cores or molds made therefrom, including a process for their manufacture.
- Binders or binder systems for foundry cores and molds are well known.
- cores or molds for making metal castings are normally prepared from a mixture of an aggregate material, such as sand, and a binding amount of a binder or binder system.
- the resultant mixture is rammed, blown, or otherwise formed to the desired shape or patterns, and then cured with the use of catalyst and/or heat to a solid, cured state.
- Resin binders used in the production of foundry molds and cores are often cured at high temperatures to achieve the fast-curing cycles required in foundries.
- resin binders have been developed which cure at a low temperature, to avoid the need for high-temperature curing operations which have higher energy requirements and which often result in the production of undesirable fumes.
- binder components are coated on the aggregate material, such as sand, and the material is blown into a box of the desired shape. Curing of the binder is carried out by passing a gaseous catalyst at ambient temperatures through the molded resin-coated material.
- the binder components normally comprise a polyhydroxy component and a polyisocyanate component. These cure to form a polyurethane in the presence of a gaseous amine catalyst.
- no-bake systems Another group of binder systems which do not require gassing or heating in order to bring about curing are known as “no-bake” systems. These “no-bake” systems also frequently employ an aggregate material, such as sand coated with a polyhydroxy component and a polyisocyanate component. In this case, the coated sand is usually mixed with a liquid tertiary amine catalyst just before the sand is placed into a holding pattern or core box, and the material is allowed to cure at ambient temperatures or slightly higher.
- an aggregate material such as sand coated with a polyhydroxy component and a polyisocyanate component.
- the coated sand is usually mixed with a liquid tertiary amine catalyst just before the sand is placed into a holding pattern or core box, and the material is allowed to cure at ambient temperatures or slightly higher.
- a binder composition comprising a polyhydroxy component, an isocyanate component having a functionality of two or more, and sufficient catalyst to catalyze substantially completely the reaction between the polyhydroxy component and the isocyanate component wherein the improvement comprises using a polyhydroxy component consisting essentially of an alkoxy modified phenolic resole resin containing at least one alkoxy methylene group for every six phenolic nuclei wherein the preponderance of the bridges joining the phenolic nuclei of said resin are ortho-ortho benzylic ether bridges.
- a moldable composition comprising aggregate material, such as foundry sand, and a binder composition comprising a polyhydroxy component, an isocyanate component having a functionality of two or more, and sufficient catalyst to catalyze substantially completely the reaction between the polyhydroxy component and the isocyanate component wherein the improvement comprises using a polyhydroxy component consisting essentially of an alkoxy modified phenolic resole resin containing at least one alkoxy methylene group for every six phenolic nuclei wherein the preponderance of the bridges joining the phenolic nuclei of said resin are ortho-ortho benzylic ether bridges.
- a process for making foundry cores or molds which comprises admixing aggregate material, such as a foundry sand or the like, and a binding amount of a binder composition comprising a polyhydroxy component, an isocyanate component having a functionality of two or more, and sufficient catalyst to catalyze substantially completely the reaction between the polyhydroxy component and the isocyanate component
- the improvement comprises using a polyhydroxy component consisting essentially of an alkoxy modified phenolic resole resin containing at least one alkoxy methylene group for every six phenolic nuclei wherein the preponderance of the bridges joining the phenolic nuclei of said resin are ortho-ortho benzylic ether bridges.
- the polyhydroxy component used in the practice of this invention is an alkoxy modified phenolic resole resin.
- This resin may be produced by heating a mixture of an aldehyde, a phenol, and a lower monohydric aliphatic alcohol in the presence of a divalent metal ion catalyst.
- the alkoxy modified resole resin may be prepared by a two-step process.
- An unmodified phenolic resole resin is prepared by heating the aldehyde and phenol in the presence of the catalyst. This resin is then modified by heating with a lower monohydric aliphatic alcohol at a pH below about 6.5 followed by dehydration to remove water produced in the reaction with the alcohol.
- the preferred method for producing the alkoxy modified phenolic resole resins used in the practice of the present invention involves reacting the phenol, the aliphatic alcohol, and aqueous formaldehyde at an elevated temperature in the presence of a divalent metal ion catalyst. Excess water is removed by evaporation under reduced pressure. If desired, the dehydrated product can be held at an elevated temperature under vacuum to increase the viscosity of the product. The resulting resin is diluted with sufficient solvent to obtain a product with the desired viscosity.
- Phenols suitable for preparing the alkoxy modified phenolic resole resins of this invention are generally any of the phenols which may be utilized in the formation of phenolic resins, and include substituted phenols, as well as unsubstituted phenol per se.
- the nature of the substituent can vary widely, and exemplary substituted phenols include alkyl-substituted phenols, aryi-substituted phenols, cycloalkyl-substituted phenols, alkenyl-substituted phenols, alkoxy-substituted phenols, aryloxy-substituted phenols, and halogen-substituted phenols.
- Suitable exemplary phenols include in addition to phenol per se, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 3,4,5-trimethyl phenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butyl phenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octyl phenol, 3,5-dicyclohexyl phenol, p-phenyl phenol, p-crotyl phenol, 3,5-dimethoxy phenol, 3,4,5-trimethoxy phenol, p-ethoxy phenol, p-butoxy phenol, 3-methyl-4-methoxy phenol, and p-phenoxy phenol.
- a preferred phenolic compound is phenol itself.
- aldehyde employed in the formation of the alkoxy modified phenolic resole resin employed in this invention can aiso vary widely. Suitable aldehydes include any of the aldehydes heretofore employed in the formation of phenolic resins, such as formaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde. In general, the aldehydes employed contain from 1 to 8 carbon atoms. The most preferred aldehyde is formaldehyde which may be used either as its aqueous solution or in its nonaqueous form as one of its solid polymers, such as paraformaldehyde.
- Alcohols useful for preparing the alkoxy modified liquid phenolic resole resins of this invention are generally primary and secondary monohydric aliphatic alcohols containing from 1 to 8 carbon atoms. Examples of useful alcohols are methanol, ethanol, n-propanol, isoproponal, n-butanol, and hexanol. Methanol is a preferred alcohol.
- Metal ion catalysts useful in production of the alkoxy modified phenolic resole resins of the present invention include saits of the divalent ions of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca, and Ba. Tetraalkoxy titanium compounds of the formula Ti(OR) 4 , where R is an alkyl group containing from 3 to 8 carbon atoms, are also useful catalysts for this reaction. A preferred catalyst is zinc acetate. These catalysts give phenolic resole resins wherein the preponderance of the bridges joining the phenolic nuclei are ortho-ortho benzylic ether bridges of the general formula --CH2(OCH2) n -- where n is a small positive integer.
- a molar excess of aldehyde per mole of phenol is used to make the resole resins of this invention. It is preferable that the molar ratio of aldehyde to phenol be in the range of from about 1.2:1 to about 2.2:1.
- alkoxy modified phenolic resole resins of the present invention sufficient alcohol is used to ensure that the alkoxy modified liquid phenolic resole resin will have at least one alkoxy methylene group for every 6 phenolic nuclei present in the resin.
- the alkoxy methylene groups have the general formula --(CH 2 O) n R where R is the alkyl group of the alcohol used, and n is a small positive integer. These groups are substituents at the positions ortho and para to the phenolic hydroxyl groups in the resin.
- the isocyanate component which can be employed in a binder according to this invention may likewise vary widely and has a functionality of 2 or more.
- exemplary of the useful isocyanates are organic polyisocyanates such as tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, and mixtures thereof, and particularly the crude mixtures thereof that are commercially available.
- polyisocyanates include methylene-bis-(4-phenyl isocyanate), n-hexyl diisocyanate, naphthalene-1,5-diisocyanate, cyclopentylene-1,3-diisocyanate, p-phenylene diisocyanate, tolylene-2,4,6-triisocyanate, and triphenylmethane-4,4',4"-triisocyanate.
- Higher isocyanates are provided by the liquid reaction products of (1) diisocyanates and (2) polyols or polyamines and the like.
- isothiocyanates and mixtures of isocyanates can be employed.
- polyaryl polyisocyanates having the following general formula: ##STR1## wherein R is selected from the group consisting of hydrogen, chlorine, bromine, alkyl groups having 1 to 5 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms; X is selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbon atoms and phenyl; and n has an average value of at least about 1 and generally about 1 to about 3.
- a typical commercially available isocyanate is polymethylene polyphenylisocyanate such as PAPI-135 sold by Upjohn Company and having a Brookfield viscosity of about 200 centipoises at 25° C., and an isocyanate equivalent of 134.
- the amounts of the polyhydroxy component and the isocyanate component employed in a binder composition of the invention are not critical and can vary widely. However, there should at least be enough of the isocyanate component present to give adequate curing of the binder.
- the isocyanate component is generally employed in a range of from about 15% to about 400% by weight, based on the weight of the polyhydroxy component, and is preferably employed in a range of from about 20 to about 200%. Moreover, while a liquid isocyanate can be used in undiluted form, so long as there is sufficient solvent employed with the polyhydroxy component, solid or viscous isocyanates can also be utilized and are generally used with an organic solvent. In this respect, the isocyanate component may include up to 80% by weight of solvent.
- both the polyhydroxy and isocyanate components are, as a practical matter, preferably dissolved in solvents in order to provide component solvent mixtures of desirable viscosity and thus facilitate the use of the same, such as in coating aggregate material with the components.
- sufficient solvents are employed to provide a Brookfield viscosity of solutions of the components which is below about 1000 centipoises and preferably less than about 300 centipoises.
- the total amount of solvent can vary widely, it is generally present in a composition of this invention in a range of from about 5% to about 70% by weight, based on total weight of the polyhydroxy component, and is preferably present in a range of from about 20% to about 60% by weight.
- the solvents employed in the practice of this invention are generally mixtures of hydrocarbon and polar organic solvents such as organic esters.
- Suitable exemplary hydrocarbon solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethyl benzene, high boiling aromatic hydrocarbon mixtures, heavy aromatic naphthas and the like. It is preferred to use hydrocarbon solvents with a flash point above 100° F.
- the compositions of this invention can be cured by both the "cold-box” and “no-bake” processes.
- the compositions are cured by means of a suitable catalyst. While any suitable catalyst for catalyzing the reaction between the phenolic resin component and isocyanate component may be used, it is to be understood that when employing the "cold-box” process the catalyst employed is generally a volatile catalyst. On the other hand, where the "no-bake” process is employed, a liquid catalyst is generally utilized. Moreover, no matter which process is utilized, that is, the "cold-box” or the "no-bake” process, at least enough catalyst is employed to cause substantially complete reaction of the polyhydroxy and isocyanate components.
- Preferred exemplary catalysts employed when curing the compositions of this invention by the "cold-box" process are volatile tertiary amine gases which are passed through a core or mold generally along with an inert carrier, such as air or carbon dioxide.
- exemplary volatile tertiary amine catalysts which result in a rapid cure at ambient temperature include trimethylamine, triethylamine and dimethylethylamine and the like.
- liquid tertiary amine catalysts are generally and preferably employed.
- Exemplary liquid tertiary amines which are basic in nature include those having a pK b value in a range of from about 4 to about 11.
- the pK b value is the negative logarithm of the dissociation constant of the base and is a well-known measure of the basicity of a basic material. The higher this number is, the weaker the base.
- Bases falling within the mentioned range are generally organic compounds containing one or more nitrogen atoms. Preferred among such materials are heterocyclic compounds containing at least one nitrogen atom in the ring structure.
- bases which have a pK b value within the range mentioned include 4-alkylpyridines wherein the alkyl group has from 1 to 4 carbon atoms, isoquinoline, arylpyridines, such as phenylpyridine, pyridine, acridine, 2-methoxypyridine, pyridazines, 3-chloropyridine, quinoline, N-methylimidazole, 4,4-dipyridine, phenylpropylpyridine, 1-methylbenzimidazole and 1,4-thiazine.
- 4-alkylpyridines wherein the alkyl group has from 1 to 4 carbon atoms isoquinoline
- arylpyridines such as phenylpyridine, pyridine, acridine, 2-methoxypyridine, pyridazines, 3-chloropyridine, quinoline, N-methylimidazole, 4,4-dipyridine, phenylpropylpyridine, 1-methylbenzimidazole
- suitable preferred catalysts include but are not limited to tertiary amine catalysts such as N,N-dimethylbenzylamine, triethylamine, tribenzylamine, N,N-dimethyl-1,3-propanediamine, N,N-dimethylethanolamine and triethanolamine. It is to be understood that various metal organic compounds can also be utilized alone as catalysts or in combination with the previously mentioned catalysts. Examples of useful metal organic compounds which may be employed as added catalytic materials are cobalt naphthenate, cobalt octoate, dibutyltin dilaurate, stannous octoate and lead naphthenate and the like. When used in combinations, such catalytic materials, that is the metal organic compounds and the amine catalysts, may be employed in all proportions with each other.
- tertiary amine catalysts such as N,N-dimethylbenzylamine, triethylamine, tribenzylamine, N,N-dimethyl-1,3-
- the amine catalysts when utilizing the compositions of this invention in the "no-bake" process, can be dissolved in suitable solvents such as, for example, the hydrocarbon solvents mentioned hereinabove.
- suitable solvents such as, for example, the hydrocarbon solvents mentioned hereinabove.
- the liquid amine catalysts are generally empioyed in a range of from about 0.5% to about 15% by weight, based on the weight of the phenolic resin component present in a composition in accordance with the invention.
- the curing time can be controlled by varying the amount of catalyst added. In general, as the amount of catalyst is increased, the cure time decreases. Furthermore, curing takes place at ambient temperature without the need for subjecting the compositions to heat, or gassing or the like.
- preheating of the sand is often employed to raise the temperature of the sand to from about 30° F. up to as high as 120° F., and preferably up to about 75° F. to 100° F. in order to accelerate the reactions and control temperature and thus provide a substantially uniform operating temperature on a day-to-day basis.
- preheating is neither critical nor necessary in carrying out the practice of this invention.
- binder compositions of this invention may be employed by admixing the same with a wide variety of particulate materials, such as limestone, calcium silicate and gravel and the like, in order to bind the same, and the admixture then manipulated in suitable fashion to form coherent shaped structures, they are particularly useful in the foundry art as binding compositions for foundry sand.
- particulate materials such as limestone, calcium silicate and gravel and the like
- the amount of binder and sand can vary widely and is not criticai.
- the binder may be present in a moldable composition, in accordance with this invention, in a range of from about 0.7% to about 6.0 % by weight based on the total weight of the composition.
- additives normally utilized in foundry manufacturing processes can also be added to the compositions during the sand coating procedure.
- Such additives include materials such as iron oxide, clay, carbohydrates, potassium fluoroborates, wood flour and the like.
- additives can be optionally used in the binder compositions of this invention.
- Such additives include, for example, organo silanes which are known coupling agents. The use of such materials may enhance the adhesion of the binder to the aggregate material.
- useful coupling agents of this type include amino silanes, epoxy silanes, mercapto silanes, hydroxy silanes and ureido silanes such as, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -hydroxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)trimethoxysilane, N- ⁇ -(amino-ethyl) ⁇ -aminopropyltrimethoxysilane and the like.
- the process for making a moldable composition comprises admixing aggregate material with at least a binding amount of the alkoxy modified phenolic resole resin component.
- the resin is dissolved in sufficient solvent to reduce the viscosity of the phenolic resinous component to below about 1000 centipoises.
- This solvent comprises hydrocarbon solvents, polar organic solvents and mixtures thereof.
- an isocyanate component having a functionality of two or more, is added and mixing is continued to uniformly coat the aggregate material with the phenolic resin and isocyanate components.
- the admixture is suitably manipulated, as for example, by distributing the same in a suitable core box or pattern.
- a sufficient amount of catalyst is added to substantially completely catalyze the reaction between the components.
- the admixture is cured forming a shaped product.
- the catalyst should generally be added to the mixture as the last constituent of the composition so that premature reaction between the components does not take place.
- the phenolic resin component can be stored separately and mixed with solvent just prior to use or, if desirable, mixed with solvent and stored until ready to use. Such is also true with the isocyanate component.
- the phenolic and isocyanate components should not be brought into contact with each other until ready to use in order to prevent any possible premature reaction between them.
- the components may be mixed with the aggregate material either simultaneously or one after the other in suitable mixing devices, such as mullers, continuous mixers, ribbon blenders and the like, while continuously stirring the admixture to insure uniform coating of aggregate particles.
- the admixture after shaping as desired is subjected to gassing with vapors of an amine catalyst. Sufficient catalyst is passed through the shaped admixture to provide substantially complete reaction between the components.
- the flow rate is dependent, of course, on the size of the shaped admixture as well as the amount of phenolic resin therein.
- the catalyst when the admixture is to be cured according to "no-bake" procedures, the catalyst is generally added to the aggregate material simultaneously while coating the aggregate material with the phenolic and isocyanate components. The admixture is then shaped and simply permitted to cure until reaction between the components is substantially complete, thus forming a shaped product such as a foundry core or mold.
- the catalyst may also be admixed with either one of the components prior to coating of the aggregate material with the components.
- a foundry core or mold comprising foundry sand and a binding amount of a binder composition comprising the reaction product of the phenolic and isocyanate components.
- a solution of the resin was used as the polyhydroxy component in foundry urethane binders. This solution was prepared by dissolving 55 g of the resin in a mixture of 20 g of dibasic ester and 25 g of aromatic hydrocarbon solvent. 0.4 g of silane A-1160 was also added. Dibasic ester, available from Du Pont, Wilmington, Del., contains approximately 25% dimethyl succinate, 50% dimethyl glutarate, and 25% dimethyl adipate. The hydrocarbon solvent is an aromatic hydrocarbon having a flash point above 100° F. The silane is sold by the Union Carbide Corp., New York, N.Y. The isocyanate solution used for the preparation of the urethane resin was prepared by dissolving 75% polymethylene polyphenylisocyanate, in 25% of the aromatic hydrocarbon solvent.
- Cores were cured at room temperature and broken after 10-minute, 1-hour, and 24-hour cure times. Tensile strengths were determined using a Detroit Testing Machine Company Model CST tester. A second portion of the sand was used to make a pyramid core. A thermometer was inserted into the core. The stripping time was determined as the time at which the core is so hard that the thermometer can no longer be pushed into the core. All samples from this and the following examples showed stripping times of 5-6 minutes. An additional amount of the coated sand was used to prepare cured 11/8-inch diameter ⁇ 2-inch cylindrical cores. The relative collapsibility of the cores was determined by placing the core specimens in a Dietert No. 785 Thermolab Dilatometer.
- a comparative test resin was prepared following the same directions as used for the resin of Example 1, except that no methanol was added to the reaction mixture. The resulting resin was somewhat more viscous than the resin of Example 1. In order to prepare a resin solution suitable for testing, 55 g of this resin was dissolved in 45 g of the dibasic ester solvent and no hydrocarbon solvent was employed.
- a second comparative test resin was Acme Bond No. 5033, a commercial phenolic resin available from the Acme Resin Corp., Forest Park, Ill.
- the results of the tests performed on the resin of this example and the two comparative test resins are given in Table I.
- the excellent hot strength of the cores prepared from the methoxy modified phenolic resole resin of the present invention is clearly shown by their superior hot distortion and dilatometer collapsibility times, when compared with those of the comparative test cores prepared from unmodified phenolic resins.
- This example illustrates use of the alkoxy modified phenolic resole resin in the "cold-box" process.
- the resin solution was prepared as in Example 1 except that the resin solution contained 1% of red oil as a release agent.
- the resole resin solution (21.5 g) and 17.6 g of the isocyanate solution were mixed with 3 kg of 410 sand using a K-45 Kitchen Aid mixer.
- the foundry mix was blown into a Redford CBT-1 core blower. Cores were blown at 50 psi air pressure and gassed 3 seconds with a 12% dimethylethylamine in CO 2 at 30 psi and then for 5 seconds with purge air at 30 psi.
- Tensile strengths were measured 1 minute, 1 hour, and 24 hours after curing using a Detroit Testing Machine Company Model CST tensile tester. Hot distortion times and dilatometer collapsibility times were also measured using the general tests described in Example 1 for cores that have been held overnight before testing.
- Example 2 illustrates the use of a substituted phenol rather than phenol per se in the formation of the alkoxy modified phenolic resole resin and its use in a "no-bake" process.
- the general procedure of Example 1 was repeated using 1317 g of p-cresol, 1185 g of 50% aqueous formaldehyde solution, 212 g of methanol, and 158 g of a 25% aqueous solution of zinc acetate. The reactants were heated at 95° C. until the free formaldehyde was 3.9%.
- the resin was cooled by dehydration under vacuum to 45° C. and a solution of 10.5 g of citric acid in 10.5 g of water was added to give a pH of 4.2.
- the resin was dehydrated under vacuum to a temperature of 95° C. and 27 inches of vacuum and held under these conditions for 1 hour.
- a comparative test resin was prepared using the same procedure except that the methanol was omitted.
- This example illustrates that the alkoxy modified phenolic resole resin can be prepared in two steps.
- the unmodified resin is first prepared and then reacted with the alcohol.
- a solution of 1.88 kg of phenol, 1.5 kg of 50% aqueous formaldehyde solution and 150 g of 25% aqueous zinc acetate solution was heated at 95° C. until the residual free formaldehyde was 3%.
- the mixture was cooled to 45° C. before the pH was adjusted to 4.3 by the addition of a solution of 10 g of citric acid and 10 g of water.
- the resin was dehydrated by heating to a temperature of 90° C. under 27 inches of vacuum.
- the flask containing the residual resin was fitted with a reflux condenser and 267 g of methanol was added slowly. Then the mixture was refluxed for 2 hours at 95° C. before vacuum was applied and the resin was then held for 3 hours at 95° C. and 27 inches of vacuum.
- a resin was prepared using the same proportions of phenol, formaldehyde and methanol except that all of the material was mixed together with the zinc acetate catalyst as in Example 1, (one-step process).
- a comparative test resin was also prepared using the same proportions of reactants except that the methanol was omitted.
- the comparative test resin and the two methoxy modified resins of this example were dissolved in solvents as in Example 1 and the resin solution was treated with the isocyanate solution and tertiary amine catalyst under the conditions given in that example.
- the results of the test on the cores prepared under these conditions are reported in Table IV. They show that the alkoxy modified resole resin prepared by the two-step process gives cores of superior hot strength to those prepared without the alkoxy modification, but they show somewhat less strength than those prepared in the one-step process using the same proportions of reactants.
Abstract
Description
TABLE I ______________________________________ Hot Dilatometer Distor- Collaps- Tensile Strength, psi tion ibility Resin Used in (Scratch Hardness) Time Time Test Cores 10 min 1 hr 24 hrs (sec) (sec) ______________________________________ Example 1 92 225 300 231 >331 (With Methoxyl (71) (84) (83) Groups) Comparative 15 63 132 72 -- Test Resin (61) (77) (79) (No Methoxyl Groups) Commercial 110 213 305 63 90 Resin (71) (78) (85) (Comparative Test) ______________________________________
TABLE II ______________________________________ Hot Dilatometer Tensile Strength, psi Distor- Collaps- (Scratch Hardness) tion ibility Resin Used in 1 24 Time Time Test Cores min 1 hr hrs (sec) (sec) ______________________________________ Methoxy Modified 122 190 210 68 140 Resole Resin (64) (71) (71) Comparative Test 137 155 168 61 92 Commercial Resin (63) (69) (70) (Without Methoxyl Groups) ______________________________________
TABLE III ______________________________________ Hot Dilatometer Tensile Strength, psi Distor- Collaps- (Scratch Hardness) tion ibility Resin Used in 10 24 Time Time Test Cores min 1 hr hrs (sec) (sec) ______________________________________ Methoxy Modified 113 213 315 65 117 p-Cresol Resole (80) (81) (86) Resin Comparative Test 138 230 325 61 84 p-Cresol Resole (83) (84) (84) (Without Methoxyl Groups) ______________________________________
TABLE IV ______________________________________ Hot Dilatometer Distortion Collapsibility Resin Used in Time Time Test Cores (sec) (sec) ______________________________________ Methoxy Modified 80 159 Resole Resin (Two-Step Process) Methoxy Modified 85 240 Resole Resin (One-Step Process) Comparative Test 73 92 (Resin Without Methoxyl Groups) ______________________________________
TABLE V ______________________________________ Molar Ratio Hot Dilatometer Phenol: Distortion Collapsibility Resin Used in Formaldehyde: Time Time Test Cores Alcohol (sec) (sec) ______________________________________ Methoxy Modified 1:1.62:0.27 86 139 1:1.62:0.54 103 404 1:1.62:0.81 90 382 1:1.62:1.62 89 229 Ethoxy Modified 1:1.62:0.54 92 298 Comparative Test 1:1.62:0 73 91 (No Alkoxyl Groups) ______________________________________
Claims (27)
Priority Applications (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/660,170 US4546124A (en) | 1984-10-12 | 1984-10-12 | Polyurethane binder compositions |
IN661/MAS/85A IN165877B (en) | 1984-10-12 | 1985-08-23 | |
AR85301465A AR242604A1 (en) | 1984-10-12 | 1985-08-30 | Polyurethane binder compositions and process for their preparation |
ZA856720A ZA856720B (en) | 1984-10-12 | 1985-09-02 | Polyurethane binder compositions and process for their preparation |
CA000491486A CA1251597A (en) | 1984-10-12 | 1985-09-25 | Polyurethane binder compositions |
ES547273A ES8703903A1 (en) | 1984-10-12 | 1985-09-25 | Polyurethane binder compositions. |
US06/781,568 US4634758A (en) | 1984-10-12 | 1985-09-30 | Process for preparing alkoxy-modified phenolic resole resins |
EP85112379A EP0177871B1 (en) | 1984-10-12 | 1985-09-30 | Polyurethane binder compositions |
DE8585112379T DE3578075D1 (en) | 1984-10-12 | 1985-09-30 | POLYURETHANE BINDER COMPOSITIONS. |
BR8504797A BR8504797A (en) | 1984-10-12 | 1985-09-30 | PROCESSES FOR THE PREPARATION OF A PHENOLIC RESOL RESIN MODIFIED BY ALCOXI AND FOR THE MANUFACTURE OF CASTING MALES OR MOLDS |
AU48154/85A AU579406B2 (en) | 1984-10-12 | 1985-10-01 | Polyurethane binder compositions and process for their preparation |
MX11485A MX114A (en) | 1984-10-12 | 1985-10-01 | COMPOSITIONS OF POLYURETHANE BINDER AND PROCEDURE FOR ITS PREPARATION |
KR1019850007307A KR930006917B1 (en) | 1984-10-12 | 1985-10-04 | Poly urethame binder composition |
JP60222013A JPS61111742A (en) | 1984-10-12 | 1985-10-07 | Polyurethane binder composition and manufacture thereof |
ES553754A ES8704366A1 (en) | 1984-10-12 | 1986-04-07 | Polyurethane binder compositions. |
US06/909,196 US4723592A (en) | 1984-10-12 | 1986-09-19 | Process for preparing foundry cores and molds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/660,170 US4546124A (en) | 1984-10-12 | 1984-10-12 | Polyurethane binder compositions |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/781,568 Continuation-In-Part US4634758A (en) | 1984-10-12 | 1985-09-30 | Process for preparing alkoxy-modified phenolic resole resins |
Publications (1)
Publication Number | Publication Date |
---|---|
US4546124A true US4546124A (en) | 1985-10-08 |
Family
ID=24648445
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/660,170 Expired - Lifetime US4546124A (en) | 1984-10-12 | 1984-10-12 | Polyurethane binder compositions |
Country Status (13)
Country | Link |
---|---|
US (1) | US4546124A (en) |
EP (1) | EP0177871B1 (en) |
JP (1) | JPS61111742A (en) |
KR (1) | KR930006917B1 (en) |
AR (1) | AR242604A1 (en) |
AU (1) | AU579406B2 (en) |
BR (1) | BR8504797A (en) |
CA (1) | CA1251597A (en) |
DE (1) | DE3578075D1 (en) |
ES (2) | ES8703903A1 (en) |
IN (1) | IN165877B (en) |
MX (1) | MX114A (en) |
ZA (1) | ZA856720B (en) |
Cited By (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4698377A (en) * | 1986-09-26 | 1987-10-06 | Acme Resin Corporation | Binder compositions containing phenolic resins and esters of alkoxy acids |
US4723592A (en) * | 1984-10-12 | 1988-02-09 | Acme Resin Corporation | Process for preparing foundry cores and molds |
WO1988001545A1 (en) * | 1986-08-25 | 1988-03-10 | Ashland Oil, Inc. | Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders |
US4848442A (en) * | 1984-10-12 | 1989-07-18 | Acme Resin Corporation | Resin binders for foundry sand cores and molds |
US4862948A (en) * | 1988-02-24 | 1989-09-05 | Borden, Inc. | Phenolic resin adhesive pastes, assemblies prepared therefrom, and processes for preparing cast metal articles using these pastes |
US4988745A (en) * | 1989-04-27 | 1991-01-29 | Acme Resin Corporation | Ester hardeners for phenolic resin binder systems |
US5036116A (en) * | 1989-04-27 | 1991-07-30 | Acme Resin Corporation | Ester hardeners for phenolic resin binder systems |
US5077323A (en) * | 1989-10-10 | 1991-12-31 | Acme Resin Corporation | Method to improve flowability of alkaline phenolic resin coated sand |
US5189079A (en) * | 1991-06-12 | 1993-02-23 | Acme Resin Corp. | Low free formaldehyde phenolic polyol formulation |
US5264535A (en) * | 1991-06-12 | 1993-11-23 | Acme Resin Corp. | Low free formaldehyde phenolic polyol formulation |
US5425994A (en) * | 1992-08-04 | 1995-06-20 | Technisand, Inc. | Resin coated particulates comprissing a formaldehyde source-metal compound (FS-MC) complex |
US5698613A (en) * | 1995-02-21 | 1997-12-16 | Mancuso Chemicals Limited | Chemical binder |
US5733952A (en) * | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
US5739255A (en) * | 1996-07-17 | 1998-04-14 | Ashland Inc. | Benzylic ether phenolic resole resins |
US5744518A (en) * | 1994-08-03 | 1998-04-28 | Borden Chemical, Inc. | Biphenyl additive for improvement in urethane foundry binders |
US5756640A (en) * | 1996-07-17 | 1998-05-26 | Ashland Inc. | Process for preparing benzylic ether phenolic resole resins |
US5908914A (en) * | 1996-07-17 | 1999-06-01 | Ashland Inc. | Benzylic ether phenolic resole resins and their uses |
AU717143B2 (en) * | 1996-07-17 | 2000-03-16 | Ashland Licensing And Intellectual Property Llc | Benzylic ether phenolic resole resins, their preparation, and uses |
WO2002022332A1 (en) * | 2000-09-13 | 2002-03-21 | Borden Chemical, Inc. | Hybrid phenol-formaldehyde and isocyanate based resins |
US20040006155A1 (en) * | 1998-11-04 | 2004-01-08 | Ashland Sudchemie Kernfest | Polyurethane based binder system for the manufacture of foundry cores and molds |
DE102004057671A1 (en) * | 2004-11-29 | 2006-06-01 | Hüttenes-Albertus Chemische Werke GmbH | Phenol formaldehyde resin comprises a mixture of phenol compound, free phenolic monomer, formaldehyde and optionally one/more phenol resin |
US20080280787A1 (en) * | 2007-05-11 | 2008-11-13 | Georgia-Pacific Chemicals Llc | Phenol-formaldehyde novolac resin having low concentration of free phenol |
US20100126690A1 (en) * | 2007-01-22 | 2010-05-27 | Arkema France | Use of amine blends for foundry shaped cores and casting metals |
EP2295482A1 (en) * | 2008-06-12 | 2011-03-16 | Hitachi Chemical Company, Ltd. | Manufacturing method for phenolic novolac resin and resin coated sand |
US20110073267A1 (en) * | 2008-05-27 | 2011-03-31 | Ashland-Südchemie-Kernfest GmbH | Coating composition which adsorbs adourous and harmful substances and is intended for the box casting of metals |
WO2012007175A1 (en) | 2010-07-16 | 2012-01-19 | Ask Chemicals L. P. | Free radical initiator compositions containing t-butyl hydroperoxide and their use |
CN102977297A (en) * | 2011-09-02 | 2013-03-20 | 中国林业科学研究院木材工业研究所 | Polyphenyleneoxide phenol formaldehyde resin and preparation method thereof, and phenol-urea-alkane resin and applications thereof |
JP2013540863A (en) * | 2010-09-30 | 2013-11-07 | エーエスケー ケミカルズ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Binder, mold material mixture and method containing substituted benzene and naphthalene for casting core and mold production |
CN104828244A (en) * | 2014-02-11 | 2015-08-12 | 苏卡斯航空电子设备有限公司 | Safety device for aircraft, and method for determining type of landing surface of aircraft |
DE102015201614A1 (en) | 2014-09-10 | 2016-03-10 | Hüttenes-Albertus Chemische Werke GmbH | Two-component binder system for the polyurethane cold box process |
US9493602B2 (en) | 2010-11-18 | 2016-11-15 | Ask Chemicals Gmbh | Polyurethaner-based binder for producing cores and casting molds using isocyanates containing a uretonimine and/or carbodiimide group, a mold material mixture containing said binder, and a method using said binder |
DE102016203896A1 (en) | 2016-03-09 | 2017-09-14 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Two-component binder system for the polyurethane cold box process |
WO2018115382A1 (en) | 2016-12-23 | 2018-06-28 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Phenol resin for use in the phenol resin component of a two-component binder system |
US11466117B2 (en) | 2016-12-23 | 2022-10-11 | Ask Chemicals Gmbh | Binder based on phenolic resins of the benzyl ether type, containing free phenol and free hydroxybenzyl alcohols |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX165850B (en) * | 1984-10-12 | 1992-12-08 | Acme Resin Corp | PHENOLIC RESIN BINDER FOR FOUNDRY AND REFRACTORY USES |
DE19850833C2 (en) * | 1998-11-04 | 2001-06-13 | Ashland Suedchemie Kernfest | Binder system for the production of cores and molds based on polyurethane, their use and method for producing a mold part based on polyurethane |
DE102006037288B4 (en) | 2006-08-09 | 2019-06-13 | Ask Chemicals Gmbh | Molding material mixture containing Cardol and / or Cardanol in foundry binders based on polyurethane, process for the preparation of a molded article and use thereof |
EP1955791A1 (en) * | 2007-01-22 | 2008-08-13 | Arkema France | Process for making foundry shaped cores and for casting metals |
DE102008007181A1 (en) | 2008-02-01 | 2009-08-06 | Ashland-Südchemie-Kernfest GmbH | Use of branched alkanediolcarboxylic diesters in polyurethane-based foundry binders |
DE102010032734A1 (en) | 2010-07-30 | 2012-02-02 | Ashland-Südchemie-Kernfest GmbH | Polyurethane-based binder system for the production of cores and molds using cyclic formals, molding mix and process |
DE102013004661A1 (en) | 2013-03-18 | 2014-09-18 | Ask Chemicals Gmbh | Use of carboxylic acids and fatty amines in PU binders for the production of cores and molds for metal casting |
DE102013004662A1 (en) | 2013-03-18 | 2014-09-18 | Ask Chemicals Gmbh | Use of monoesters of epoxidized fatty acids in PU binders for the production of cores and molds for metal casting |
DE102013004663A1 (en) | 2013-03-18 | 2014-09-18 | Ask Chemicals Gmbh | Epoxy compounds and fatty acid esters as constituents of polyurethane-based foundry binders |
JP5850288B1 (en) * | 2014-04-10 | 2016-02-03 | Dic株式会社 | Process for producing alkoxylated resol type phenolic resin, alkoxylated resol type phenolic resin, resin composition and paint |
DE102014110189A1 (en) | 2014-07-18 | 2016-01-21 | Ask Chemicals Gmbh | CO catalysts for polyurethane cold box binders |
DE102014117284A1 (en) | 2014-11-25 | 2016-05-25 | Ask Chemicals Gmbh | Polyurethane binder system for producing cores and casting molds, molding material mixture containing the binder and a method using the binder |
DE102015102952A1 (en) | 2015-03-02 | 2016-09-08 | Ask Chemicals Gmbh | Process for curing polyurethane binders in molding material mixtures by introducing tertiary amines and solvents and kit for carrying out the process |
DE102015107016A1 (en) | 2015-05-05 | 2016-06-23 | Ask Chemicals Gmbh | Process for reducing free formaldehyde in benzyl ether resins |
WO2017075351A1 (en) | 2015-10-30 | 2017-05-04 | Ask Chemicals, L.P. | Polyurethane binder containing alcohol solvent |
DE102016202795A1 (en) | 2016-02-23 | 2017-08-24 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Use of a composition as a binder component for the preparation of feeder elements by the cold-box process, corresponding processes and feeder elements |
RU177159U1 (en) * | 2016-11-21 | 2018-02-12 | Юрий Мурадович Погосбекян | INSTALLATION FOR ELECTRIC PROCESSING OF CASTING BINDING MATERIAL |
DE102016123621A1 (en) | 2016-12-06 | 2018-06-07 | Ask Chemicals Gmbh | Polyurethane binder with improved flowability |
DE102018100694A1 (en) | 2018-01-12 | 2019-07-18 | Ask Chemicals Gmbh | Formaldehyde-reduced phenolic resin binder |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2079633A (en) * | 1935-12-17 | 1937-05-11 | Du Pont | Synthetic resins |
US3409579A (en) * | 1966-08-01 | 1968-11-05 | Ashland Oil Inc | Foundry binder composition comprising benzylic ether resin, polyisocyanate, and tertiary amine |
US3676392A (en) * | 1971-01-26 | 1972-07-11 | Ashland Oil Inc | Resin compositions |
US3894981A (en) * | 1974-01-30 | 1975-07-15 | Anatoly Abramovich Kruglikov | Method of producing phenolic moulding materials |
US4079031A (en) * | 1976-07-14 | 1978-03-14 | Delta Oil Products Corporation | Improved foundry process and binder resin composition therefor |
US4116916A (en) * | 1976-10-26 | 1978-09-26 | International Minerals & Chemical Corp. | Foundry resin components |
US4317896A (en) * | 1980-12-10 | 1982-03-02 | International Minerals & Chemical Corp. | Foundry no-bake combination resin binder |
US4358570A (en) * | 1979-09-28 | 1982-11-09 | Mitsubishi Petrochemical Company Limited | Binder composition for foundry sand molds |
US4436881A (en) * | 1983-06-29 | 1984-03-13 | Acme Resin Corporation | Polyurethane binder compositions |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1118143A (en) * | 1975-11-13 | 1982-02-09 | Aristo Corporation | Foundry resin components |
US4179427A (en) * | 1978-03-21 | 1979-12-18 | Ashland Oil, Inc. | Phenolic resin-polyisocyanate binders |
US4311631A (en) * | 1979-09-20 | 1982-01-19 | Delta Oil Products Corporation | Low emission foundry binder system |
JPS5867712A (en) * | 1981-10-20 | 1983-04-22 | Dainippon Ink & Chem Inc | Preparation of phenolic foam having improved heat insulating preformance |
US4448951A (en) * | 1983-01-17 | 1984-05-15 | Basf Wyandotte Corporation | Phenolic polyols and rigid cellular compositions derived therefrom |
-
1984
- 1984-10-12 US US06/660,170 patent/US4546124A/en not_active Expired - Lifetime
-
1985
- 1985-08-23 IN IN661/MAS/85A patent/IN165877B/en unknown
- 1985-08-30 AR AR85301465A patent/AR242604A1/en active
- 1985-09-02 ZA ZA856720A patent/ZA856720B/en unknown
- 1985-09-25 ES ES547273A patent/ES8703903A1/en not_active Expired
- 1985-09-25 CA CA000491486A patent/CA1251597A/en not_active Expired
- 1985-09-30 EP EP85112379A patent/EP0177871B1/en not_active Expired - Lifetime
- 1985-09-30 BR BR8504797A patent/BR8504797A/en not_active IP Right Cessation
- 1985-09-30 DE DE8585112379T patent/DE3578075D1/en not_active Expired - Lifetime
- 1985-10-01 MX MX11485A patent/MX114A/en unknown
- 1985-10-01 AU AU48154/85A patent/AU579406B2/en not_active Ceased
- 1985-10-04 KR KR1019850007307A patent/KR930006917B1/en not_active IP Right Cessation
- 1985-10-07 JP JP60222013A patent/JPS61111742A/en active Granted
-
1986
- 1986-04-07 ES ES553754A patent/ES8704366A1/en not_active Expired
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2079633A (en) * | 1935-12-17 | 1937-05-11 | Du Pont | Synthetic resins |
US3409579A (en) * | 1966-08-01 | 1968-11-05 | Ashland Oil Inc | Foundry binder composition comprising benzylic ether resin, polyisocyanate, and tertiary amine |
US3726867A (en) * | 1966-08-01 | 1973-04-10 | Ashland Oil Inc | Foundry process and articles produced thereby |
US3676392A (en) * | 1971-01-26 | 1972-07-11 | Ashland Oil Inc | Resin compositions |
US3894981A (en) * | 1974-01-30 | 1975-07-15 | Anatoly Abramovich Kruglikov | Method of producing phenolic moulding materials |
US4079031A (en) * | 1976-07-14 | 1978-03-14 | Delta Oil Products Corporation | Improved foundry process and binder resin composition therefor |
US4116916A (en) * | 1976-10-26 | 1978-09-26 | International Minerals & Chemical Corp. | Foundry resin components |
US4358570A (en) * | 1979-09-28 | 1982-11-09 | Mitsubishi Petrochemical Company Limited | Binder composition for foundry sand molds |
US4317896A (en) * | 1980-12-10 | 1982-03-02 | International Minerals & Chemical Corp. | Foundry no-bake combination resin binder |
US4436881A (en) * | 1983-06-29 | 1984-03-13 | Acme Resin Corporation | Polyurethane binder compositions |
Cited By (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4723592A (en) * | 1984-10-12 | 1988-02-09 | Acme Resin Corporation | Process for preparing foundry cores and molds |
US4848442A (en) * | 1984-10-12 | 1989-07-18 | Acme Resin Corporation | Resin binders for foundry sand cores and molds |
WO1988001545A1 (en) * | 1986-08-25 | 1988-03-10 | Ashland Oil, Inc. | Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders |
US4760101A (en) * | 1986-08-25 | 1988-07-26 | Ashland Oil, Inc. | Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders |
US4698377A (en) * | 1986-09-26 | 1987-10-06 | Acme Resin Corporation | Binder compositions containing phenolic resins and esters of alkoxy acids |
AU591792B2 (en) * | 1986-09-26 | 1989-12-14 | Borden Chemical, Inc. | Binder compositions containing phenolic resins and esters of alkoxy acids |
US4862948A (en) * | 1988-02-24 | 1989-09-05 | Borden, Inc. | Phenolic resin adhesive pastes, assemblies prepared therefrom, and processes for preparing cast metal articles using these pastes |
US4988745A (en) * | 1989-04-27 | 1991-01-29 | Acme Resin Corporation | Ester hardeners for phenolic resin binder systems |
US5036116A (en) * | 1989-04-27 | 1991-07-30 | Acme Resin Corporation | Ester hardeners for phenolic resin binder systems |
US5077323A (en) * | 1989-10-10 | 1991-12-31 | Acme Resin Corporation | Method to improve flowability of alkaline phenolic resin coated sand |
US5189079A (en) * | 1991-06-12 | 1993-02-23 | Acme Resin Corp. | Low free formaldehyde phenolic polyol formulation |
US5264535A (en) * | 1991-06-12 | 1993-11-23 | Acme Resin Corp. | Low free formaldehyde phenolic polyol formulation |
US5425994A (en) * | 1992-08-04 | 1995-06-20 | Technisand, Inc. | Resin coated particulates comprissing a formaldehyde source-metal compound (FS-MC) complex |
US5744518A (en) * | 1994-08-03 | 1998-04-28 | Borden Chemical, Inc. | Biphenyl additive for improvement in urethane foundry binders |
US5792802A (en) * | 1994-08-03 | 1998-08-11 | Borden Chemical, Inc. | Biphenyl additive for improvement in urethane foundry binders |
US5852071A (en) * | 1994-08-03 | 1998-12-22 | Borden Chemical, Inc. | Biphenyl additive for improvement in urethane foundry binders |
US5698613A (en) * | 1995-02-21 | 1997-12-16 | Mancuso Chemicals Limited | Chemical binder |
US5733952A (en) * | 1995-10-18 | 1998-03-31 | Borden Chemical, Inc. | Foundry binder of phenolic resole resin, polyisocyanate and epoxy resin |
US5981622A (en) * | 1995-10-18 | 1999-11-09 | Borden Chemical, Inc. | Foundry binder of polyurethane, phenolic resin, polyisocyanate and epoxy resin |
US5739255A (en) * | 1996-07-17 | 1998-04-14 | Ashland Inc. | Benzylic ether phenolic resole resins |
US5756640A (en) * | 1996-07-17 | 1998-05-26 | Ashland Inc. | Process for preparing benzylic ether phenolic resole resins |
US5908914A (en) * | 1996-07-17 | 1999-06-01 | Ashland Inc. | Benzylic ether phenolic resole resins and their uses |
AU717143B2 (en) * | 1996-07-17 | 2000-03-16 | Ashland Licensing And Intellectual Property Llc | Benzylic ether phenolic resole resins, their preparation, and uses |
US20040006155A1 (en) * | 1998-11-04 | 2004-01-08 | Ashland Sudchemie Kernfest | Polyurethane based binder system for the manufacture of foundry cores and molds |
US6772820B2 (en) * | 1998-11-04 | 2004-08-10 | Ashland Inc. | Polyurethane based binder system for the manufacture of foundry cores and molds |
AU2001259276B2 (en) * | 2000-09-13 | 2005-09-01 | Bayer Corporation | Hybrid phenol-formaldehyde and isocyanate based resins |
US20030092855A1 (en) * | 2000-09-13 | 2003-05-15 | Miller Todd R. | Hybrid phenol-formaldehyde and polymeric isocyanate based adhesive and methods of synthesis and use |
US6478998B1 (en) | 2000-09-13 | 2002-11-12 | Borden Chemical, Inc. | Hybrid phenol-formaldehyde and polymeric isocyanate based adhesive and methods of synthesis and use |
WO2002022332A1 (en) * | 2000-09-13 | 2002-03-21 | Borden Chemical, Inc. | Hybrid phenol-formaldehyde and isocyanate based resins |
DE102004057671A1 (en) * | 2004-11-29 | 2006-06-01 | Hüttenes-Albertus Chemische Werke GmbH | Phenol formaldehyde resin comprises a mixture of phenol compound, free phenolic monomer, formaldehyde and optionally one/more phenol resin |
DE102004057671B4 (en) * | 2004-11-29 | 2007-04-26 | Hüttenes-Albertus Chemische Werke GmbH | Phenol-formaldehyde resins and process for their preparation |
US20100126690A1 (en) * | 2007-01-22 | 2010-05-27 | Arkema France | Use of amine blends for foundry shaped cores and casting metals |
US10828696B2 (en) | 2007-01-22 | 2020-11-10 | Arkema France | Use of amine blends for foundry shaped cores and casting metals |
US20080280787A1 (en) * | 2007-05-11 | 2008-11-13 | Georgia-Pacific Chemicals Llc | Phenol-formaldehyde novolac resin having low concentration of free phenol |
US9458349B2 (en) | 2007-05-11 | 2016-10-04 | Georgia-Pacific Chemicals Llc | Phenol-formaldehyde novolac resin having low concentration of free phenol |
US8778495B2 (en) | 2007-05-11 | 2014-07-15 | Gerogia-Pacific Chemicals LLC | Phenol-formaldehyde novolac resin having low concentration of free phenol |
US20110073267A1 (en) * | 2008-05-27 | 2011-03-31 | Ashland-Südchemie-Kernfest GmbH | Coating composition which adsorbs adourous and harmful substances and is intended for the box casting of metals |
US8215373B2 (en) | 2008-05-27 | 2012-07-10 | Ask Chemicals Gmbh | Coating composition which adsorbs adourous and harmful substances and is intended for the box casting of metals |
EP2295482A4 (en) * | 2008-06-12 | 2013-11-27 | Hitachi Chemical Co Ltd | Manufacturing method for phenolic novolac resin and resin coated sand |
KR20110028277A (en) * | 2008-06-12 | 2011-03-17 | 히다치 가세고교 가부시끼가이샤 | Manufacturing method for phenolic novolac resin and resin-coated sand |
EP2295482A1 (en) * | 2008-06-12 | 2011-03-16 | Hitachi Chemical Company, Ltd. | Manufacturing method for phenolic novolac resin and resin coated sand |
WO2012007175A1 (en) | 2010-07-16 | 2012-01-19 | Ask Chemicals L. P. | Free radical initiator compositions containing t-butyl hydroperoxide and their use |
JP2013540863A (en) * | 2010-09-30 | 2013-11-07 | エーエスケー ケミカルズ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Binder, mold material mixture and method containing substituted benzene and naphthalene for casting core and mold production |
US9000067B2 (en) | 2010-09-30 | 2015-04-07 | Ask Chemicals Gmbh | Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method |
US9493602B2 (en) | 2010-11-18 | 2016-11-15 | Ask Chemicals Gmbh | Polyurethaner-based binder for producing cores and casting molds using isocyanates containing a uretonimine and/or carbodiimide group, a mold material mixture containing said binder, and a method using said binder |
CN102977297B (en) * | 2011-09-02 | 2014-09-17 | 中国林业科学研究院木材工业研究所 | Polyphenyleneoxide phenol formaldehyde resin and preparation method thereof, and phenol-urea-alkane resin and applications thereof |
CN102977297A (en) * | 2011-09-02 | 2013-03-20 | 中国林业科学研究院木材工业研究所 | Polyphenyleneoxide phenol formaldehyde resin and preparation method thereof, and phenol-urea-alkane resin and applications thereof |
CN104828244A (en) * | 2014-02-11 | 2015-08-12 | 苏卡斯航空电子设备有限公司 | Safety device for aircraft, and method for determining type of landing surface of aircraft |
DE102015201614A1 (en) | 2014-09-10 | 2016-03-10 | Hüttenes-Albertus Chemische Werke GmbH | Two-component binder system for the polyurethane cold box process |
DE102016203896A1 (en) | 2016-03-09 | 2017-09-14 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Two-component binder system for the polyurethane cold box process |
WO2017153474A1 (en) | 2016-03-09 | 2017-09-14 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Two-component binder system for the polyurethane cold-box process |
WO2018115382A1 (en) | 2016-12-23 | 2018-06-28 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Phenol resin for use in the phenol resin component of a two-component binder system |
DE102016125624A1 (en) | 2016-12-23 | 2018-06-28 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Phenolic resin for use in the phenolic resin component of a two component binder system |
EP3854829A1 (en) | 2016-12-23 | 2021-07-28 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Phenolic resin for use in the phenolic resin component of a two-component binder system |
US11230623B2 (en) | 2016-12-23 | 2022-01-25 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Phenol resin for use in the phenol resin component of a two-component binder system |
US11466117B2 (en) | 2016-12-23 | 2022-10-11 | Ask Chemicals Gmbh | Binder based on phenolic resins of the benzyl ether type, containing free phenol and free hydroxybenzyl alcohols |
Also Published As
Publication number | Publication date |
---|---|
ES553754A0 (en) | 1987-04-01 |
ES8704366A1 (en) | 1987-04-01 |
CA1251597A (en) | 1989-03-21 |
KR930006917B1 (en) | 1993-07-24 |
AR242604A1 (en) | 1993-04-30 |
AU579406B2 (en) | 1988-11-24 |
BR8504797A (en) | 1986-07-22 |
AU4815485A (en) | 1986-04-17 |
EP0177871B1 (en) | 1990-06-06 |
KR860003284A (en) | 1986-05-23 |
ES547273A0 (en) | 1987-03-01 |
IN165877B (en) | 1990-02-03 |
MX114A (en) | 1993-08-01 |
EP0177871A3 (en) | 1987-05-13 |
ES8703903A1 (en) | 1987-03-01 |
EP0177871A2 (en) | 1986-04-16 |
DE3578075D1 (en) | 1990-07-12 |
ZA856720B (en) | 1986-04-30 |
JPS61111742A (en) | 1986-05-29 |
JPH0441692B2 (en) | 1992-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4546124A (en) | Polyurethane binder compositions | |
KR100299817B1 (en) | Urethane Casting Binder with Water Resistance | |
EP0183782B1 (en) | Phenolic resin-polyisocyanate binder systems | |
US4698377A (en) | Binder compositions containing phenolic resins and esters of alkoxy acids | |
US4436881A (en) | Polyurethane binder compositions | |
US3632844A (en) | Non-sticking sand mix for foundry cores | |
US4982781A (en) | No-bake process for preparing foundry shapes for casting low melting metal castings | |
US5189079A (en) | Low free formaldehyde phenolic polyol formulation | |
US4946876A (en) | Polyurethane-forming foundry binders containing a polyester polyol | |
US4246157A (en) | Binder compositions containing phenolic resins and organic phosphate and/or carbonate solvents | |
US5101001A (en) | Polyurethane-forming foundry binders and their use | |
US6365646B1 (en) | Method to improve humidity resistance of phenolic urethane foundry binders | |
US4634758A (en) | Process for preparing alkoxy-modified phenolic resole resins | |
US4852629A (en) | Cold-box process for forming foundry shapes which utilizes certain carboxylic acids as bench life extenders | |
US4760101A (en) | Polyurethane-forming binder compositions containing certain carboxylic acids as bench life extenders | |
US5264535A (en) | Low free formaldehyde phenolic polyol formulation | |
US4723592A (en) | Process for preparing foundry cores and molds | |
US5132339A (en) | Polyurethane-forming foundry binders containing a polyether polyol | |
US5874487A (en) | Foundary binder systems which contain alcohol modified polyisocyanates | |
US6013695A (en) | Foundry binders containing modified polyisocyanates | |
USRE34092E (en) | Phenolic resin compositions and their use in foundry binders | |
WO2002060985A1 (en) | Phenolic urethane foundry binders containing methyl benzoate | |
US4814363A (en) | Phenolic resin compositions and their use in foundry binders | |
US4852636A (en) | Process for preparing foundry shapes and castings utilizing certain polyurethane binders | |
WO2005009647A2 (en) | Stabilized phenolic resole resin compositions and their use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ACME RESIN CORPORATION 1401 CIRCLE AVENUE FOREST P Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:LAITAR, ROBERT A.;GOMEZ, EDUARDO;REEL/FRAME:004325/0456 Effective date: 19841011 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
CC | Certificate of correction | ||
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: BORDEN, INC., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ACME RESIN CORPORATION;REEL/FRAME:006747/0482 Effective date: 19931025 |
|
AS | Assignment |
Owner name: BORDEN CHEMICAL, INC., OHIO Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BORDEN, INC.;REEL/FRAME:008000/0363 Effective date: 19960611 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: HA-INTERNATIONAL, LLC, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BORDEN CHEMICAL, INC.;REEL/FRAME:013000/0956 Effective date: 20020517 |
|
AS | Assignment |
Owner name: BANK ONE, NA, ILLINOIS Free format text: SECURITY AGREEMENT;ASSIGNOR:HA-INTERNATIONAL, LLC;REEL/FRAME:014313/0590 Effective date: 20040128 |
|
AS | Assignment |
Owner name: HA-INTERNATIONAL, LLC, ILLINOIS Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (SUCCESSOR BY MERGER TO BANK ONE, N.A.), AS AGENT;REEL/FRAME:039113/0551 Effective date: 20160620 |